CN109950552A - A kind of nitrogen-doped carbon porous hollow C catalyst and its preparation method and application - Google Patents
A kind of nitrogen-doped carbon porous hollow C catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN109950552A CN109950552A CN201910267071.0A CN201910267071A CN109950552A CN 109950552 A CN109950552 A CN 109950552A CN 201910267071 A CN201910267071 A CN 201910267071A CN 109950552 A CN109950552 A CN 109950552A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- catalyst
- doped carbon
- porous hollow
- carbon porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a kind of nitrogen-doped carbon porous hollow C catalysts and its preparation method and application, the catalyst the preparation method comprises the following steps: imidazoles substance is mixed with zinc salt after be added in alcohol solution, it stirs evenly, it stands, filtering, drying, obtained solid powder is add to deionized water, ultrasonic mixing is uniform, obtains mixed liquor A；Aqueous solutions of organic acids highly basic is adjusted into pH to 7-9, obtains mixed liquid B；Mixed liquor A and mixed liquid B mixing, after mixing evenly, it is centrifuged, dries, obtain the solid powder of Adsorption organic acid root anion, the solid powder of Adsorption organic acid root anion is put into tube furnace with ionic liquid again, the high-temperature calcination under high-purity atmosphere finally obtains the nitrogen-doped carbon porous hollow C catalyst.Nitrogen-doped carbon porous hollow C catalyst prepared by the present invention, has high electro catalytic activity, and superpower stability is better than business platinum carbon by verifying the performance of electrochemical reduction oxygen of catalyst of the invention.
Description
Technical field
The present invention relates to a kind of nitrogen-doped carbon porous hollow C catalysts and its preparation method and application.
Background technique
The big topic of two that 21 century is eternally immutable: the energy and environmental crisis；This affects the ecology in the whole world, economy, and
The existence of the mankind.Last century, traditional fossil energy support the development of whole mankind's economy and industrial sector so far, and fossil fires now
Material it is exhausted and depleted, irreversible environmental disruption will be caused；Vicious circle if things go on like this is directly threatened and is landed
The harmonious coexistence of ball and the mankind.Under energy consumption and the Double jeopardy of environmental pollution, fuel cell as emerging green technology,
If one brush single spark obtains extensive concern in scientific circles, become the replacer of the following power source.
Under acid condition, the excessively high active current potential of cathode causes ORR rate slow, need to be reduced with cathod catalyst
The activated energy barrier of O=O key fracture, to promote the ORR rate on battery electrode surface.The use of cathod catalyst is considered as
Influence the leading factor of fuel cell electrochemical effects.At present under acid condition, having high catalytic activity has platinum and platinum alloy.
However, a series of efficient platinum catalyst there is valences defects such as high, rare, low stability and weak mithridatism, restrict so far
The development and application of fuel cell.In alkaline electrolyte, the dynamics of hydrogen reduction is obviously easier than in acidic electrolyte bath, in addition to
Outside noble metal platinum and its alloy there are also transition metal (Fe, Co, Mn) nitride, contain hetero atom carbon material.
Under acid condition, ORR has higher hydrogen reduction potential, and the metal platinum and its alloy Yin Qiang that catalytic activity is high
Expensive cost of manufacture is limited.Under alkaline condition, exploitation transition metal is urged using carbon material containing hetero atom as cathodic oxygen reduction
Agent.Transition metal is restricted due to its stability and activity problems in use.Contain hetero atom carbon material
Since more difficult, the active not high problem of the construction of active sites exists.
Therefore, the primary restraining factors of the commercialized development of electrochemical reduction oxygen be electrode material catalyst it is at high cost and
How service life short problem develops a kind of electrode material catalyst of electrochemical reduction oxygen that cost is relatively low, performance is stable, is
The research emphasis of electrochemical reduction oxygen.
Summary of the invention
For above-mentioned technical problem of the existing technology, the purpose of the present invention is to provide a kind of nitrogen-doped carbon porous airs
Heart C catalyst and its preparation method and application, not only preparation cost is low for catalyst of the invention, is applied to electrochemical reduction oxygen
In gas, stability is good, active height.
A kind of preparation method of the nitrogen-doped carbon porous hollow C catalyst, it is characterised in that the following steps are included:
1) imidazoles substance is mixed with zinc salt with 1-4: 1 mass ratio, mixture is then added in alcohol solution, and stirring is equal
It after even, stands, filtering, drying, obtains solid powder；
2) 0.15-0.45 g solid powder obtained by step 1) is added in 10-30 mL deionized water, ultrasonic mixing is uniform, obtains
Mixed liquor A；The aqueous solutions of organic acids highly basic that concentration is 0.03-0.1 g/mL is adjusted into pH to 7-9, obtains mixed liquid B；
3) mixed liquor A in step 2 and mixed liquid B are mixed with 0.2-0.5: 1 volume ratio, after mixing evenly, through centrifugation point
From, it is dry, obtain the solid powder of Adsorption organic acid root anion；
4) step 3) obtained solid powder is uniformly mixed with ionic liquid with 1-5: 1 mass ratio, mixture places into pipe
In formula furnace, high-temperature calcination under Yu Gaochun atmosphere, calcination time 1-3h finally obtains the nitrogen-doped carbon porous hollow carbon and urges
Agent.
The preparation method of a kind of nitrogen-doped carbon porous hollow C catalyst, it is characterised in that described in step 1)
Zinc salt is zinc nitrate, zinc sulfate or zinc chloride, preferably zinc nitrate or zinc chloride；Imidazoles substance is methylimidazole, 2- methyl
Imidazoles, 1,2- methylimidazole, 4-methylimidazole, 1,2- dimethyl -5- nitroimidazole or Dimetridazole, preferably 2- methyl
Imidazoles or DMIZ 1,2 dimethylimidazole；The alcohols solvent is ethyl alcohol, methanol, ethylene glycol or butanol, preferably methanol or ethyl alcohol.
The preparation method of a kind of nitrogen-doped carbon porous hollow C catalyst, it is characterised in that described in step 2
Organic acid is tannic acid, benzoic acid or acetic acid, preferably tannic acid；Highly basic is sodium hydroxide, potassium hydroxide, magnesium hydroxide or hydrogen
Calcium oxide, preferably sodium hydroxide or potassium hydroxide.
The preparation method of a kind of nitrogen-doped carbon porous hollow C catalyst, it is characterised in that described in step 4)
Ionic liquid is 1- butyl -3- methyl imidazolium tetrafluoroborate, 1- ethoxy -3- methylimidazole dintrile amine salt or 1- vinyl -
3- methylimidazole dintrile amine salt, preferably 1- butyl -3- methyl imidazolium tetrafluoroborate.
The preparation method of a kind of nitrogen-doped carbon porous hollow C catalyst, it is characterised in that high-purity in step 4)
The gas of atmosphere is ammonia, nitrogen, argon gas, helium or air, preferably nitrogen or argon gas；The gas of high-purity atmosphere is passed through
Flow velocity in tube furnace is 30-60 mL/min.
A kind of preparation method of the nitrogen-doped carbon porous hollow C catalyst, it is characterised in that in step 4), high temperature
The temperature of calcining is 700-950 DEG C.
A kind of preparation method of the nitrogen-doped carbon porous hollow C catalyst, it is characterised in that in step 1), imidazoles
The ratio between quality and the volume of alcohols solvent of substance are 1:10-40, and the unit of quality is g, and the unit of volume is mL.
The nitrogen-doped carbon porous hollow C catalyst prepared according to the method described above.
Application of the nitrogen-doped carbon porous hollow C catalyst in electrocatalytic oxidation reduction reaction.
Application of the nitrogen-doped carbon porous hollow C catalyst in electrocatalytic oxidation reduction reaction, it is characterised in that with
Electrochemical workstation is as electrochemistry generating device, using the nitrogen-doped carbon porous hollow C catalyst as working electrode, with
Graphite rod is used as to electrode, and silver/silver chlorate is as reference electrode, using the KOH aqueous solution of 0.05-0.2 mol/L as electrolyte,
Carry out electrochemical oxygen reduction reaction.
Compared with the existing technology, the beneficial effect that the present invention obtains is:
1) when the present invention is reacted for traditional platinum and its alloy catalyst for electrochemical reduction oxygen, platinum and its alloy preparation
Problem at high cost and poor stability has invented nitrogen-doped carbon porous hollow C catalyst and its preparation method and application.This hair
In bright catalyst preparation process, zinc salt is coated by imidazoles substance first, then in water and organic acid reaction, imidazoles object
The zinc and organic acid anion binding on matter surface layer combine, so that imidazoles substance surface layer obtains zinc and organic acid anion
(so that when high-temperature calcination imidazoles substance is carbonized, surface layer will not collapse stable bond object, keep good and urge
Agent structure), form solid powder.
2) during the present invention prepares nitrogen-doped carbon porous hollow carbon, in ionic liquid as creation defect qualitative object
Under effect, solid powder is made to form porous deficiency carbon material during the preparation process.By control optimization solid powder and from
The mass ratio of sub- liquid and the calcination temperature in tube furnace, so as to obtain a series of nitrogen containing different degrees of deficiency
Adulterate porous hollow C catalyst.During tube furnace calcining, the imidazoles substance containing nitrogen occurs carbonization and obtains
Nitrogen-doped carbon material, the zinc salt inside imidazoles substance vaporize at high temperature, so that the original zinc of nitrogen-doped carbon material internal
Position forms hollow structure, and gaseous zinc salt passes through nitrogen-doped carbon material surface and its surface layer is made to form porous structure, to mention
The delivery rate of high substance, organic anion also occur to be carbonized at high temperature and add to N doping porous hollow carbon surface.
Ionic liquid may further destroy carbon material in zinc gasification and obtain defect more abundant simultaneously during calcining
Pore structure more abundant is formed, so that it is more advantageous to mass transfer, the quick progress of reaction.
3) when pure carbon material of the invention activates in high temperature process furnances, the nitrogenous small organic molecule under ionic liquid effect
While forming nitrogenous carbon material, different type nitrogen defect is also formed, and this nitrogen defect plays pole in catalytic reaction process
Its important role.Zinc gasification and ionic liquid make nitrogenous material form hollow porous structure during corroding.Relatively
In traditional platinum catalyst, the preparation condition of catalyst of the present invention is relatively simple, at low cost；And your gold catalyst of the present invention is free of
Category and transition metal, get rid of the use of noble metal and transition metal.
4) nitrogen-doped carbon porous hollow C catalyst prepared by the present invention has high electro catalytic activity, superpower stabilization
Property, hence it is evident that reduce the energy barrier of electrochemical reduction oxygen.By the property for verifying the electrochemical reduction oxygen of catalyst of the invention
It can be better than business platinum carbon (the platinum carbon catalyst of 20 percent platinum load capacity)；Catalyst of the invention can completely disengage making for platinum
With.Cost is relatively low for catalyst preparation integrated artistic, is advantageous to industrialized production, has broad application prospects.
Detailed description of the invention
Fig. 1 is the electrochemical oxygen reduction of nitrogen-doped carbon porous hollow C catalyst prepared by embodiment 1 ~ 3 and business platinum carbon
Linear sweep voltammetry figure；
Fig. 2 is the linear scan volt of the electrochemical oxygen reduction of nitrogen-doped carbon porous hollow C catalyst prepared by embodiment 2,4,5
Antu；
Fig. 3 is that TEM schemes under 50 nm scale of nitrogen-doped carbon porous hollow C catalyst prepared by embodiment 2；
Fig. 4 is that TEM schemes under 20 nm scale of nitrogen-doped carbon porous hollow C catalyst prepared by embodiment 2.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1:
Prepare nitrogen-doped carbon porous hollow C catalyst, comprising the following steps:
1) 2-methylimidazole being mixed with zinc nitrate with the mass ratio of 2:1, mixture is then added in methanol, after mixing evenly,
24 hours are stood, filtering, obtains solid powder at drying；Wherein the ratio between the quality of 2-methylimidazole and the volume of methanol are 1:20,
The unit of quality is g, and the unit of volume is mL.
2) 0.15 g solid powder obtained by step 1) is added in 10 mL deionized waters, ultrasonic mixing is uniform, must mix
Liquid A.The tannin aqueous acid sodium hydroxide that concentration is 0.04 g/mL is adjusted into pH to 9, obtains mixed liquid B.
3) mixed liquor A obtained by step 2 and mixed liquid B are mixed with the volume ratio of 0.3:1, stirs 8 min, then carries out
Centrifuge separation, drying, obtain the solid powder of absorbing tannin acid radical anion.
4) step 3) obtained solid powder and 1- butyl -3- methyl imidazolium tetrafluoroborate is mixed with 5: 1 mass ratio
It closes uniformly, mixture places into tube furnace, and (it is 40 that nitrogen, which is passed through the flow velocity in tube furnace, for calcining under high pure nitrogen atmosphere
ML/min), using room temperature as initial temperature, 900 DEG C is warming up to the heating rate of 3 DEG C/min, then calcines 2h at 900 DEG C,
Finally obtain nitrogen-doped carbon porous hollow C catalyst.
Electrochemical reduction oxygen tests (test of nitrogen-doped carbon porous hollow C catalyst):
Rotating disk electrode (r.d.e), electrochemical workstation are as electrochemistry generating device.Nitrogen-doped carbon prepared by 4 mg embodiments 1 is more
The hollow C catalyst in hole is dispersed in the nafion ethanol solution that 1mL mass fraction is 0.5%, after ultrasonic disperse is uniform, pipettes 4
UL dispersant liquid drop dries in rotating disk electrode (r.d.e), uses as working electrode.
Using graphite rod as to electrode, silver/silver chlorate is as reference electrode, using the KOH aqueous solution of 0.1mol/L as electricity
Liquid is solved, and is passed through oxygen into electrolyte.Test voltage is 0.2 ~ 1.2V voltage range, and sweeping the rate of hastening is 10 mV/S.Carry out electricity
The linear sweep voltammetry figure of chemical oxygen reduction reaction, electrochemical oxygen reduction is as shown in Figure 1.
Electrochemical oxygen reduction tests (test of business platinum carbon):
Rotating disk electrode (r.d.e), electrochemical workstation are as electrochemistry generating device.By the business platinum carbon of 4 mg platinum mass fractions 20%
It is dispersed in the nafion ethanol solution that 1mL mass fraction is 0.5%, after ultrasonic disperse is uniform, pipettes 5 uL dispersant liquid drops and revolving
Turn to dry on disk electrode, be used as working electrode.
Using graphite rod as to electrode, silver/silver chlorate is as reference electrode, using the KOH aqueous solution of 0.1mol/L as electricity
Liquid is solved, and is passed through oxygen into electrolyte.Test voltage is 0.2 ~ 1.2V voltage range, and sweeping the rate of hastening is 10 mV/S.Carry out electricity
The linear sweep voltammetry figure of chemical oxygen reduction reaction, electrochemical oxygen reduction is as shown in Figure 1.
Embodiment 2:
Prepare nitrogen-doped carbon porous hollow C catalyst, comprising the following steps:
1) 2-methylimidazole being mixed with zinc nitrate with the mass ratio of 2:1, mixture is then added in methanol, after mixing evenly,
24 hours are stood, filtering, obtains solid powder at drying；Wherein the ratio between the quality of 2-methylimidazole and the volume of methanol are 1:20,
The unit of quality is g, and the unit of volume is mL.
2) 0.15 g solid powder obtained by step 1) is added in 10 mL deionized waters, ultrasonic mixing is uniform, must mix
Liquid A.The tannin aqueous acid sodium hydroxide that concentration is 0.04 g/mL is adjusted into pH to 9, obtains mixed liquid B.
3) mixed liquor A obtained by step 2 and mixed liquid B are mixed with the volume ratio of 0.3:1, stirs 8 min, then carries out
Centrifuge separation, drying, obtain the solid powder of absorbing tannin acid radical anion.
4) step 3) obtained solid powder and 1- butyl -3- methyl imidazolium tetrafluoroborate is mixed with 3: 1 mass ratio
It closes uniformly, mixture places into tube furnace, and (it is 40 that nitrogen, which is passed through the flow velocity in tube furnace, for calcining under high pure nitrogen atmosphere
ML/min), using room temperature as initial temperature, 900 DEG C is warming up to the heating rate of 3 DEG C/min, then calcines 2h at 900 DEG C,
Finally obtain nitrogen-doped carbon porous hollow C catalyst.Nitrogen-doped carbon porous hollow C catalyst manufactured in the present embodiment is 50
TEM figure under nm and 20nm is as shown in Figure 3 and Figure 4 respectively, as can be seen that hollow structure is presented in catalyst from Fig. 3 and Fig. 4,
The hollow structure of catalyst is conducive to the transmission of substance, improves active catalyst sites exposure, makes full use of active site.
The experiment of electrochemical reduction oxygen:
Rotating disk electrode (r.d.e), electrochemical workstation are as electrochemistry generating device.Nitrogen-doped carbon prepared by 4 mg embodiments 2 is more
The hollow C catalyst in hole is dispersed in the nafion ethanol solution that 1mL mass fraction is 0.5%, after ultrasonic disperse is uniform, pipettes 4
UL dispersant liquid drop dries in rotating disk electrode (r.d.e), uses as working electrode.
Using graphite rod as to electrode, silver/silver chlorate is as reference electrode, using the KOH aqueous solution of 0.1mol/L as electricity
Liquid is solved, and is passed through oxygen into electrolyte.Test voltage is 0.2 ~ 1.2V voltage range, and sweeping the rate of hastening is 10 mV/S.Carry out electricity
The linear sweep voltammetry figure of chemical oxygen reduction reaction, electrochemical oxygen reduction is as depicted in figs. 1 and 2.
Embodiment 3:
Prepare nitrogen-doped carbon porous hollow C catalyst, comprising the following steps:
1) 2-methylimidazole being mixed with zinc nitrate with the mass ratio of 2:1, mixture is then added in methanol, after mixing evenly,
24 hours are stood, filtering, obtains solid powder at drying；Wherein the ratio between the quality of 2-methylimidazole and the volume of methanol are 1:20,
The unit of quality is g, and the unit of volume is mL.
2) 0.15 g solid powder obtained by step 1) is added in 10 mL deionized waters, ultrasonic mixing is uniform, must mix
Liquid A.It is that 0.04 g/mL tannin aqueous acid sodium hydroxide adjusts pH to 9 by concentration, obtains mixed liquid B.
3) mixed liquor A obtained by step 2 and mixed liquid B are mixed with the volume ratio of 0.3:1, stirs 8 min, then carries out
Centrifuge separation, drying, obtain the solid powder of absorbing tannin acid radical anion.
4) step 3) obtained solid powder and 1- butyl -3- methyl imidazolium tetrafluoroborate is mixed with 1: 1 mass ratio
It closes uniformly, mixture places into tube furnace, and (it is 40 that nitrogen, which is passed through the flow velocity in tube furnace, for calcining under high pure nitrogen atmosphere
ML/min), using room temperature as initial temperature, 900 DEG C is warming up to the heating rate of 3 DEG C/min, then calcines 2h at 900 DEG C,
Finally obtain nitrogen-doped carbon porous hollow C catalyst.
The experiment of electrochemical reduction oxygen:
Rotating disk electrode (r.d.e), electrochemical workstation are as electrochemistry generating device.Nitrogen-doped carbon prepared by 4 mg embodiments 3 is more
The hollow C catalyst in hole is dispersed in the nafion ethanol solution that 1mL mass fraction is 0.5%, after ultrasonic disperse is uniform, pipettes 4
UL dispersant liquid drop dries in rotating disk electrode (r.d.e), uses as working electrode.
Using graphite rod as to electrode, silver/silver chlorate is as reference electrode, using the KOH aqueous solution of 0.1mol/L as electricity
Liquid is solved, and is passed through oxygen into electrolyte.Test voltage is 0.2 ~ 1.2V voltage range, and sweeping the rate of hastening is 10 mV/S.Carry out electricity
The linear sweep voltammetry figure of chemical oxygen reduction reaction, electrochemical oxygen reduction is as shown in Figure 1.
Embodiment 4:
Prepare nitrogen-doped carbon porous hollow C catalyst, comprising the following steps:
1) 2-methylimidazole being mixed with zinc nitrate with the mass ratio of 2:1, mixture is then added in methanol, after mixing evenly,
24 hours are stood, filtering, drying obtain solid powder；Wherein the ratio between the quality of 2-methylimidazole and the volume of methanol are 1:20,
The unit of quality is g, and the unit of volume is mL.
2) 0.15 g solid powder obtained by step 1) is added in 10 mL deionized waters, ultrasonic mixing is uniform, must mix
Liquid A.The tannin aqueous acid sodium hydroxide that concentration is 0.04 g/mL is adjusted into pH to 9, obtains mixed liquid B.
3) mixed liquor A obtained by step 2 and mixed liquid B are mixed with the volume ratio of 0.3:1, stirs 8 min, then carries out
Centrifuge separation, drying, obtain the solid powder of absorbing tannin acid radical anion.
4) step 3) obtained solid powder and 1- butyl -3- methyl imidazolium tetrafluoroborate is mixed with 3: 1 mass ratio
It closes uniformly, mixture places into tube furnace, and (it is 40 that nitrogen, which is passed through the flow velocity in tube furnace, for calcining under high pure nitrogen atmosphere
ML/min), using room temperature as initial temperature, 800 DEG C is warming up to the heating rate of 3 DEG C/min, then calcines 2h at 800 DEG C,
Finally obtain nitrogen-doped carbon porous hollow C catalyst.
The experiment of electrochemical reduction oxygen:
Rotating disk electrode (r.d.e), electrochemical workstation are as electrochemistry generating device.Nitrogen-doped carbon prepared by 4 mg embodiments 4 is more
The hollow C catalyst in hole is dispersed in the nafion ethanol solution that 1mL mass fraction is 0.5%, after ultrasonic disperse is uniform, pipettes 4
UL dispersant liquid drop dries in rotating disk electrode (r.d.e), uses as working electrode.
Using graphite rod as to electrode, silver/silver chlorate is as reference electrode, using the KOH aqueous solution of 0.1mol/L as electricity
Liquid is solved, and is passed through oxygen into electrolyte.Test voltage is 0.2 ~ 1.2V voltage range, and sweeping the rate of hastening is 10 mV/S.Carry out electricity
The linear sweep voltammetry figure of chemical oxygen reduction reaction, electrochemical oxygen reduction is as shown in Figure 2.
Embodiment 5:
Prepare nitrogen-doped carbon porous hollow C catalyst, comprising the following steps:
1) 2-methylimidazole being mixed with zinc nitrate with the mass ratio of 2:1, mixture is then added in methanol, after mixing evenly,
24 hours are stood, filtering, drying obtain solid powder；Wherein the ratio between the quality of 2-methylimidazole and the volume of methanol are 1:20,
The unit of quality is g, and the unit of volume is mL.
2) 0.15 g solid powder obtained by step 1) is added in 10 mL deionized waters, ultrasonic mixing is uniform, must mix
Liquid A.The tannin aqueous acid sodium hydroxide that concentration is 0.04 g/mL is adjusted into pH to 9, obtains mixed liquid B.
3) mixed liquor A obtained by step 2 and mixed liquid B are mixed with the volume ratio of 0.3:1, stirs 8 min, then carries out
Centrifuge separation, drying, obtain the solid powder of absorbing tannin acid radical anion.
4) step 3) obtained solid powder and 1- butyl -3- methyl imidazolium tetrafluoroborate is mixed with 3: 1 mass ratio
It closes uniformly, mixture places into tube furnace, and (it is 40 that nitrogen, which is passed through the flow velocity in tube furnace, for calcining under high pure nitrogen atmosphere
ML/min), using room temperature as initial temperature, 700 DEG C is warming up to the heating rate of 3 DEG C/min, then calcines 2h at 700 DEG C,
Finally obtain nitrogen-doped carbon porous hollow C catalyst.
The experiment of electrochemical reduction oxygen:
Rotating disk electrode (r.d.e), electrochemical workstation are as electrochemistry generating device.Nitrogen-doped carbon prepared by 4 mg embodiments 5 is more
The hollow C catalyst in hole is dispersed in the nafion ethanol solution that 1mL mass fraction is 0.5%, after ultrasonic disperse is uniform, pipettes 4
UL dispersant liquid drop dries in rotating disk electrode (r.d.e), uses as working electrode.
Using graphite rod as to electrode, silver/silver chlorate is as reference electrode, using the KOH aqueous solution of 0.1mol/L as electricity
Liquid is solved, and is passed through oxygen into electrolyte.Test voltage is 0.2 ~ 1.2V voltage range, and sweeping the rate of hastening is 10 mV/S.Carry out electricity
The linear sweep voltammetry figure of chemical oxygen reduction reaction, electrochemical oxygen reduction is as shown in Figure 2.
What LSV curve was shown is the performance of ORR, and ORR is electrochemical oxygen reduction reaction, and take-off potential is got over closer to 1
Good, half wave potential is better closer to 1, and limiting current density is the bigger the better.
It will be seen from figure 1 that the LSV of different degrees of defect and different calcination temperatures prepared by the embodiment of the present invention 1 ~ 5
Curve is best in example 2, and is better than the platinum carbon of business, i.e., with the catalytic performance of superior electrochemical oxygen reduction.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (10)
1. a kind of preparation method of nitrogen-doped carbon porous hollow C catalyst, it is characterised in that the following steps are included:
1) imidazoles substance is mixed with zinc salt with 1-4: 1 mass ratio, mixture is then added in alcohol solution, and stirring is equal
It after even, stands, filtering, drying, obtains solid powder；
2) 0.15-0.45 g solid powder obtained by step 1) is added in 10-30 mL deionized water, ultrasonic mixing is uniform, obtains
Mixed liquor A；The aqueous solutions of organic acids highly basic that concentration is 0.03-0.1 g/mL is adjusted into pH to 7-9, obtains mixed liquid B；
3) mixed liquor A in step 2 and mixed liquid B are mixed with 0.2-0.5: 1 volume ratio, after mixing evenly, through centrifugation point
From, it is dry, obtain the solid powder of Adsorption organic acid root anion；
4) step 3) obtained solid powder is uniformly mixed with ionic liquid with 1-5: 1 mass ratio, mixture places into pipe
In formula furnace, high-temperature calcination under Yu Gaochun atmosphere, calcination time 1-3h finally obtains the nitrogen-doped carbon porous hollow carbon and urges
Agent.
2. a kind of preparation method of nitrogen-doped carbon porous hollow C catalyst as described in claim 1, it is characterised in that step
1) in, the zinc salt is zinc nitrate, zinc sulfate or zinc chloride, preferably zinc nitrate or zinc chloride；Imidazoles substance is methyl miaow
Azoles, 2-methylimidazole, 1,2- methylimidazole, 4-methylimidazole, 1,2- dimethyl -5- nitroimidazole or Dimetridazole, it is excellent
It is selected as 2-methylimidazole or DMIZ 1,2 dimethylimidazole；The alcohols solvent is ethyl alcohol, methanol, ethylene glycol or butanol, preferably first
Alcohol or ethyl alcohol.
3. a kind of preparation method of nitrogen-doped carbon porous hollow C catalyst as described in claim 1, it is characterised in that step
2) in, the organic acid is tannic acid, benzoic acid or acetic acid, preferably tannic acid；Highly basic is sodium hydroxide, potassium hydroxide, hydrogen
Magnesia or calcium hydroxide, preferably sodium hydroxide or potassium hydroxide.
4. a kind of preparation method of nitrogen-doped carbon porous hollow C catalyst as described in claim 1, it is characterised in that step
4) in, the ionic liquid be 1- butyl -3- methyl imidazolium tetrafluoroborate, 1- ethoxy -3- methylimidazole dintrile amine salt or
1- vinyl -3- methylimidazole dintrile amine salt, preferably 1- butyl -3- methyl imidazolium tetrafluoroborate.
5. a kind of preparation method of nitrogen-doped carbon porous hollow C catalyst as described in claim 1, it is characterised in that step
4) in, the gas of high-purity atmosphere is ammonia, nitrogen, argon gas, helium or air, preferably nitrogen or argon gas；High-purity atmosphere
Gas inlet pipe formula furnace in flow velocity be 30-60 mL/min.
6. a kind of preparation method of nitrogen-doped carbon porous hollow C catalyst as described in claim 1, it is characterised in that step
4) in, the temperature of high-temperature calcination is 700-950 DEG C.
7. a kind of preparation method of nitrogen-doped carbon porous hollow C catalyst as described in claim 1, it is characterised in that step
1) in, the ratio between quality and the volume of alcohols solvent of imidazoles substance are 1:10-40, and the unit of quality is g, and the unit of volume is
mL。
8. nitrogen-doped carbon porous hollow C catalyst prepared by the method as described in claim 1 ~ 7 any one.
9. application of the nitrogen-doped carbon porous hollow C catalyst as claimed in claim 8 in electrocatalytic oxidation reduction reaction.
10. application as claimed in claim 9, it is characterised in that using electrochemical workstation as electrochemistry generating device, with institute
Nitrogen-doped carbon porous hollow C catalyst is stated as working electrode, using graphite rod as to electrode, silver/silver chlorate is as reference electricity
Pole carries out electrochemical oxygen reduction reaction using the KOH aqueous solution of 0.05-0.2 mol/L as electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910267071.0A CN109950552B (en) | 2019-04-03 | 2019-04-03 | Nitrogen-doped carbon porous hollow carbon catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910267071.0A CN109950552B (en) | 2019-04-03 | 2019-04-03 | Nitrogen-doped carbon porous hollow carbon catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109950552A true CN109950552A (en) | 2019-06-28 |
| CN109950552B CN109950552B (en) | 2020-07-14 |
Family
ID=67013648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910267071.0A Active CN109950552B (en) | 2019-04-03 | 2019-04-03 | Nitrogen-doped carbon porous hollow carbon catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109950552B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110639591A (en) * | 2019-10-12 | 2020-01-03 | 苏州大学 | Indium zinc sulfide loaded on nitrogen-doped carbon hollow sphere, preparation method thereof and application thereof in wastewater treatment |
| CN110773218A (en) * | 2019-10-08 | 2020-02-11 | 中国科学院兰州化学物理研究所 | Nitrogen-doped biochar-loaded metal nickel catalyst and application thereof |
| CN111987326A (en) * | 2020-08-25 | 2020-11-24 | 中国石油大学(华东) | Superfine M-N-C non-noble metal carbon-based oxygen reduction catalyst, preparation method and application |
| CN112751008A (en) * | 2021-02-09 | 2021-05-04 | 福州大学 | Polyphenol modified zinc-iron based heterojunction oxide carbon nano lithium ion battery cathode composite material and preparation method thereof |
| CN113070040A (en) * | 2021-04-22 | 2021-07-06 | 浙江工业大学 | Carbon material-loaded ionic liquid adsorption material for removing carbonyl sulfide and application thereof |
| CN113809340A (en) * | 2021-07-30 | 2021-12-17 | 五邑大学 | Preparation method of efficient and stable porous M-N-C catalyst |
| CN113839058A (en) * | 2021-09-23 | 2021-12-24 | 重庆文理学院 | Carbon-based oxygen reduction reaction catalyst and preparation method thereof |
| CN114142049A (en) * | 2021-11-26 | 2022-03-04 | 武汉科思特仪器股份有限公司 | Preparation method and application of hollow carbon-based oxygen reduction electrocatalyst |
| CN117954643A (en) * | 2024-03-26 | 2024-04-30 | 淄博火炬能源有限责任公司 | Heteropoly acid-based nitrogen-doped carbon catalyst material, preparation method thereof and method for preparing zinc-air battery by using same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285900A (en) * | 2013-05-14 | 2013-09-11 | 广东精进能源有限公司 | Method for preparing carbon and nitrogen doped titanium dioxide by utilizing ionic liquid |
| CN106115653A (en) * | 2016-06-22 | 2016-11-16 | 兰州理工大学 | A kind of preparation method of the porous carbon materials of Heteroatom doping |
| CN107834078A (en) * | 2017-09-27 | 2018-03-23 | 山西大学 | A kind of exotic atom adulterates cellular porous carbon material and preparation method thereof |
| CN109267326A (en) * | 2018-07-20 | 2019-01-25 | 华中科技大学 | Multi-element doping carbon nano pipe array modifying carbon fibers and the preparation method and application thereof |
-
2019
- 2019-04-03 CN CN201910267071.0A patent/CN109950552B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285900A (en) * | 2013-05-14 | 2013-09-11 | 广东精进能源有限公司 | Method for preparing carbon and nitrogen doped titanium dioxide by utilizing ionic liquid |
| CN106115653A (en) * | 2016-06-22 | 2016-11-16 | 兰州理工大学 | A kind of preparation method of the porous carbon materials of Heteroatom doping |
| CN107834078A (en) * | 2017-09-27 | 2018-03-23 | 山西大学 | A kind of exotic atom adulterates cellular porous carbon material and preparation method thereof |
| CN109267326A (en) * | 2018-07-20 | 2019-01-25 | 华中科技大学 | Multi-element doping carbon nano pipe array modifying carbon fibers and the preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 余江英等: "质子交换膜燃料电池氮掺杂碳基催化剂研究进展", 《材料导报Ａ：综述篇》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110773218A (en) * | 2019-10-08 | 2020-02-11 | 中国科学院兰州化学物理研究所 | Nitrogen-doped biochar-loaded metal nickel catalyst and application thereof |
| CN110639591B (en) * | 2019-10-12 | 2022-07-19 | 苏州大学 | Indium zinc sulfide loaded on nitrogen-doped carbon hollow sphere, preparation method thereof and application thereof in wastewater treatment |
| CN110639591A (en) * | 2019-10-12 | 2020-01-03 | 苏州大学 | Indium zinc sulfide loaded on nitrogen-doped carbon hollow sphere, preparation method thereof and application thereof in wastewater treatment |
| CN111987326A (en) * | 2020-08-25 | 2020-11-24 | 中国石油大学(华东) | Superfine M-N-C non-noble metal carbon-based oxygen reduction catalyst, preparation method and application |
| CN111987326B (en) * | 2020-08-25 | 2022-12-20 | 中国石油大学(华东) | Ultrafine M-N-C non-noble metal carbon-based oxygen reduction catalyst, preparation method and application |
| CN112751008A (en) * | 2021-02-09 | 2021-05-04 | 福州大学 | Polyphenol modified zinc-iron based heterojunction oxide carbon nano lithium ion battery cathode composite material and preparation method thereof |
| CN112751008B (en) * | 2021-02-09 | 2022-06-03 | 福州大学 | Polyphenol modified zinc-iron based heterojunction oxide carbon nano lithium ion battery cathode composite material and preparation method thereof |
| CN113070040A (en) * | 2021-04-22 | 2021-07-06 | 浙江工业大学 | Carbon material-loaded ionic liquid adsorption material for removing carbonyl sulfide and application thereof |
| CN113809340A (en) * | 2021-07-30 | 2021-12-17 | 五邑大学 | Preparation method of efficient and stable porous M-N-C catalyst |
| CN113839058A (en) * | 2021-09-23 | 2021-12-24 | 重庆文理学院 | Carbon-based oxygen reduction reaction catalyst and preparation method thereof |
| CN113839058B (en) * | 2021-09-23 | 2023-05-26 | 重庆文理学院 | Carbon-based oxygen reduction reaction catalyst and preparation method thereof |
| CN114142049A (en) * | 2021-11-26 | 2022-03-04 | 武汉科思特仪器股份有限公司 | Preparation method and application of hollow carbon-based oxygen reduction electrocatalyst |
| CN114142049B (en) * | 2021-11-26 | 2024-06-07 | 武汉科思特仪器股份有限公司 | Preparation method and application of hollow carbon-based oxygen reduction electrocatalyst |
| CN117954643A (en) * | 2024-03-26 | 2024-04-30 | 淄博火炬能源有限责任公司 | Heteropoly acid-based nitrogen-doped carbon catalyst material, preparation method thereof and method for preparing zinc-air battery by using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109950552B (en) | 2020-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109950552A (en) | A kind of nitrogen-doped carbon porous hollow C catalyst and its preparation method and application | |
| CN102088091A (en) | Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof | |
| CN107267124A (en) | A kind of nitrogenous graphitized carbon material containing the bimetallic MOFs of Ni/Fe | |
| CN108067248B (en) | PtNi alloy catalyst with three-dimensional nanorod structure and preparation and application thereof | |
| CN109174157B (en) | Preparation method of cobalt-nitrogen co-doped biomass carbon oxidation reduction catalyst | |
| CN111244470B (en) | Nano composite cathode and preparation and application thereof | |
| CN105107541A (en) | Preparing method for high-activity and high-stability composite catalyst for fuel cells | |
| CN109713326A (en) | The porous carbon coating eight of Heteroatom doping vulcanizes the application of nine cobalt composite catalysts | |
| CN103949251A (en) | Oxygen reduction catalyst as well as preparation method and application of oxygen reduction catalyst | |
| CN112968185A (en) | Preparation method of plant polyphenol modified manganese-based nano composite electrocatalyst with supermolecular network framework structure | |
| CN106058276A (en) | Preparation method of silica-modified multi-spherical-cavity carbon material and application of carbon material to fuel cell membrane electrode | |
| CN110038638A (en) | A kind of iron load nitrogen-doped porous carbon material and its synthetic method and application with excellent electro-catalysis reduction nitrogen performance | |
| CN110350213B (en) | High-efficiency PtRu/C bifunctional fuel cell anode catalyst and preparation method thereof | |
| CN109659571B (en) | Carbon dioxide electrochemical reduction catalyst and application thereof in zero-distance reactor | |
| CN102368558A (en) | Electrode catalyst composition, electrode and fuel cell and membrane-electrode assembly each comprising the electrode | |
| CN102723503A (en) | Direct-methanol fuel cell anode catalyst and preparation method | |
| CN107293759A (en) | A kind of preparation method of fuel cell oxygen reduction electrocatalyst | |
| CN104241664A (en) | PtM/M'-PPy-C electrocatalyst for oxygen reduction reaction of fuel cell and preparation method of electrocatalyst | |
| CN103594718A (en) | Preparation and usage of nanoribbon-shaped Cucurbit[6]uril carried cubic palladium nanoparticles | |
| CN108565474B (en) | Synthetic method of iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance | |
| CN105742654A (en) | Preparation method for mixed-phase mullite electrocatalyst and catalyst layer used for negative electrode of fuel cell | |
| CN103120960B (en) | Pt-Nafion/C catalyst and preparation method and application for same | |
| CN111229195A (en) | Electro-reduction carbon dioxide catalytic material and preparation and application thereof | |
| CN106328958A (en) | Preparation method for membrane electrode of alkali anion exchange membrane fuel cell | |
| CN112259750B (en) | Preparation method and application of polyion liquid functionalized cobalt-nitrogen loaded foamed nickel composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |